KR0118112B1 - Process for producing thermoplastic polyester resin foam - Google Patents

Abstract

No content.

Description

Manufacturing method of thermoplastic polyester resin foam

1 to 3 are cross-sectional views of the apparatus required for the reheating operation of the present invention.

4 is a schematic diagram of one example of an apparatus required for continuously performing a reheating operation according to the present invention.

5 is a graph showing the results of 2 in the test of the present invention.

6 is a front view of a food container according to the present invention.

7 is a plan view of a food container according to the present invention.

8, 9 and 10 are electron micrographs showing the cell shape of the foams prepared in Examples 9, 12 and 17, respectively.

* Explanation of symbols for main parts of the drawings

1: foam 2: hydrothermal

3: metal gauge 4: steam

5: extruder 6: steam tank

8: burner 9: container

10: winder

[Industrial use]

The present invention relates to a production method by extrusion of thermoplastic polyester resin foam and to a product of thermoplastic polyester resin foam.

The manufacturing method of the present invention provides a fine cell molded uniformly with high expansion rate, and does not cause colored contamination on the foam even in a continuous extrusion process.

The present invention also relates to a thermoplastic polyester resin foam sheet having excellent thermoforming.

The polyester resin foam of the present invention is low in density and strong in spite of light weight.

In addition, the foam of the present invention can be widely used because it is excellent in heat resistance, chemical resistance, thermal ductility and impact absorption.

In particular, the polyester resin foam is suitable for use as a material capable of thermoforming into a heat resistant food container.

[Prior art]

Thermoplastic polyester-based resins such as polyethylene terephthalate and polybutylene terephthalate have excellent mechanical properties, heat resistance, chemical resistance and dimensional stability, and thus are widely used in injection molded products, oils, and films.

However, during melting, the thermoplastic polyester-based resin is difficult to obtain viscoelastic properties so that foaming properties can be obtained, and thus it is difficult to obtain an excellent foam in which a foaming agent easily escapes during foam extrusion and uniformly molded dense microcells.

In order to solve this problem, in the foam extrusion of an aromatic polyester type, the method of adding diglycidyl ester to an aromatic polyester was proposed.

(JP-B-61-4849, where "JP-B" means Japanese Patent Publication)

In the foam extrusion of the thermoplastic polyester system, a method of adding a diglycidyl ester and a polyhydric carboxylic anhydride to the thermoplastic polyester system has been proposed in order to personalize the melt viscosity of the thermoplastic polyester system.

(JP-A-59-210955, where JP-A refers to an unexamined Japanese patent application)

The inventors have been engaged in the production and research of foam extrusion for many years and have experienced the fact that the foamed extrusion material of thermoplastic polyester mixed with diglycidyl ester compound is discolored in a continuous process.

In addition, the present inventors do not use any diglycidyl ester compound with 2 pyromellitic diangydride, and when the thermoplastic polyester is mixed, the foam is not colored even if the foam extrusion is continuously performed for a long time. I found it to be discontinuous. Furthermore, the inventors of the present invention have found that when adding a compounding compound containing two or more acid anhydride groups per molecule, such as a compound of Group I, Group II, or Group III metals on the periodic table, to the thermoplastic polyester resin, With the improvement of chronicity, it has been found that foams with high tensile ductility and finer cells are formed.

JP-A59-135237 (US Pat. Nos. 4,462,947 and 4,466,843, European Patent 0151162A) discloses that a polyester resin foam can be thermoformed with a heat resistant food container that can be applied to a double oven.

However, when only polycarbonate is mixed, carbon dioxide liberated in polycarbonate as well as low melt viscosity is used as a blowing agent, and when used as a cooking vessel of this heating or food in a microwave oven due to its low expansion rate and poor heat resistance, You cannot hold a heated container with your bare hands.

[Problem to Solve Invention]

The inventors found thermoplastic polyester-based resin foaming sites with their expansion rate, good thermal insulation and very good thermoforming in this study.

Accordingly, it is a first object of the present invention to provide a method for producing a highly expanded thermoplastic polyester resin foam by adjusting viscoelasticity during melting of an extrusion expanded molded body of thermoplastic polyester resin.

It is a second object of the present invention to provide a method for producing a thermoplastic polyester resin foam which does not cause colored contamination even when continuously performing long-term operation of the extrusion expanded molded article of the thermoplastic polyester resin.

A third object of the present invention is to provide a method for producing a thermoplastic polyester resin foam having a uniform fine cell in extrusion molding of a thermoplastic polyester resin.

A fourth object of the present invention is to provide a thermoplastic polyester resin foam having numerous tensile strengths and elongation in extrusion molding.

It is a fifth object of the present invention to provide a method for producing a thermoplastic polyester resin foam having high expandability and excellent heat resistance by post-expansion treatment by reheating an extruded expanded thermoplastic polyester resin foam.

A sixth object of the present invention is to provide a method for producing an extruded foam sheet having excellent moldability such as thermoforming of a thermoplastic polyester resin.

A seventh object of the present invention is to obtain an extruded foam sheet of thermoplastic polyester resin through thermoforming, and to provide a heat resistant food container which can be applied to an oven.

The present invention is to achieve the above object, the point is as follows.

(1) A compound containing at least two acid anhydride groups per molecule is added to the thermoplastic polyester resin, and the thermoplastic polyester resin is melted and the mixture of the blowing agent mixed with the molten resin is extruded to a low pressure paper to form. A method for producing a thermoplastic thermoplastic resin foam comprising performing.

(2) Molecules, two or more acid anhydride groups and compounds of Group I, II, III metals on the periodic table are added to the thermoplastic polyester resin, and the thermoplastic polyester resin is melted, and a blowing agent is added to the molten resin. A method for producing a thermoplastic polyester resin foam in which a mixture is extruded to a low pressure paper to perform molding.

(3) A thermoplastic polyester system which cools the high temperature thermoplastic polyester resin foam to a temperature lower than the glass transition point of the resin immediately after expansion so that the crystallinity is within 30%, and then heats the polyester resin foam at 60 ° C or higher. Method for producing a resin foam.

(4) A thermoplastic polyester resin foam sheet which is an extrusion foam sheet of a thermoplastic polyester resin and has a molecular orientation ratio of 4.5 or less and a crystallinity of less than 20% in terms of foam sheet.

(5) A food container manufactured by bonding a non-foamed film of thermoplastic resin to at least one side of the thermoplastic polyester resin foam sheet to obtain a laminated seal, and thermoforming the sheet into a container so that the non-foamed film is located inside. .

[Means to solve the problem]

In the production of the polyester resin foam of the present invention, an extruder was used.

The thermoplastic polyester resin was pressurized inside the extruder to melt and extruded through a die with a low pressure support to produce a foam.

In the production of the polyester resin foam of the present invention, a compound containing two or more acid anhydride groups per molecule was added to the thermoplastic polyester resin.

Due to the addition of compounds containing two or more acid anhydride groups per molecule, the viscoelasticity of the thermoplastic polyester resin is improved during extrusion, so that the vaporized foam can be maintained inside the dense cell, and evenly distributed fine cells are formed. Can be.

As the compound containing two or more acid anhydride groups per molecule is bonded to the hydroxyl group of the molecular chain of the thermoplastic polyester resin so that a crosslinking bond occurs naturally, the viscoelasticity of the thermoplastic polyester can be improved during extrusion.

The term viscoelasticity during melting can be identified by the phenomenon of swelling or retraction from the exit of the die when the melt is extruded through the die, and can generally be expressed as a die expansion rate.

Die expansion rate is measured when the molten resin is extruded through a round orifice die containing circular portions, and the die expansion rate was calculated by the following equation.

Die expansion rate is an important factor in extrusion molding.

A die expansion ratio of 2-5 is preferred in order to obtain moldings with large cross-sectional areas and, in particular, microcells with uniform distribution.

In the present invention, a thermoplastic polyester resin and a compound containing two or more acid anhydride groups are mixed and melted in an extruder, and then a blowing agent is sprayed in contact with the molten mixture by injecting the molten mixture through the die of the molding extruder. Extruded to prepare a blowing agent.

In another embodiment of the present invention, a compound containing two or more acid anhydride groups per molecule and a Group I, II, III metal compound on the periodic table were added to the thermoplastic polyester resin.

The foam was prepared by feeding the mixed material to the extruder in the same manner as described above.

By adding the periodic table of Group I, II, III metal compounds, a thermoplastic polyester resin foam having a fine cell with uniform distribution can be obtained.

The thermoplastic polyester resins used in the present invention are linear polyesters of polyvalent condensates of aromatic dicarboxylic acid components and diol components. Examples of the dicarboxylic acid component used in the present invention include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl ether carboxylic acid, diphenyl sulfone dicarboxylic acid and diphenoxy ethanedicarboxylic acid.

Examples of the diol component used in the present invention include ethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, cyclohexane dimethane, tricyclodecane dimethane, and 2,2-bis (4- β-hydroxyethoxyphenyl) propane, 4,4-bis (β-hydroxyethoxy) diphenylsulfone, diethylene glycol and 1,4-butanediol.

Polyethylene terephthalate, polybutylene terephthalate, polybutylene terephthalate elastomer, amorphous polyethylene naphthalate polyester, polycyclohexane terephthalate and mixtures thereof are used as polyesters containing dicarboxylic acid and diol components. It is desirable to.

Modified resins composed of at least 50% of thermoplastic polyester resins can be used.

Aromatic acid anhydrides having at least two or more acid anhydride groups per molecule, acid anhydrides substituted with halogens, and the like can be used as components containing two or more acid anhydride groups per molecule. Also mixtures of modified compounds with the above conditions can be used.

2-part pyromellitic acid, benzophenol tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride and 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl- 3-cyclohexene-1,2-dicarboxylic dianhydride etc. are preferable.

Among these, especially anhydrous pyromellitic acid is preferable.

It is preferable to use the amount of 0.05 parts by weight to 5.0 parts by weight based on 100 parts by weight of the foam polyester resin as a compound containing two or more acid anhydrides per molecule.

When the amount of the compound having two or more acid anhydride groups per molecule is less than 0.05 part by weight relative to 100 parts by weight of the thermoplastic polyester resin, it is insufficient to improve the viscoelasticity of the thermoplastic polyester resin during extrusion and an excellent foaming agent cannot be formed.

On the other hand, when it exceeds 5.0 parts by weight, the molten material of the thermoplastic polyester resin is advanced to be ineffective in compression molding. Any one of inorganic and organic compounds having a metal as a constituent atom may be used as a metal compound of Groups I, II, and III on the periodic table.

Examples of inorganic compounds include potassium chloride, sodium chloride, sodium bicarbonate, sodium carbonate, potassium carbonate, zinc carbonate, magnesium carbonate, calcium carbonate, aluminum carbonate, sodium oxide, potassium oxide, zinc oxide, magnesium oxide, calcium oxide, aluminum oxide, and these And hydroxides of metals.

Examples of the organic compounds include sodium stearate, potassium stearate, aluminum stearate, sodium montanate, calcium montanate, lithium acetate, zinc acetate, sodium acetate, magnesium acetate, calcium acetate, sodium caprylate, zinc caprylate, ka Magnesium phthalate, calcium caprylate, sodium caprylate, calcium myristic acid, aluminum myristic acid, calcium benzoate, potassium terephthalate, sodium terephthalate, sodium ethoxylated, potassium phenoxylate and the like. Among these, metal compounds of group I or group II on the periodic table are preferable, and group I metal compounds are particularly preferable.

By using a compound of a Group I, II or III metal, it is possible to increase the viscoelastic effect as a compound having two or more acid anhydride groups per molecule as well as cell production of finer thermoplastic polyester resin foams.

The compound of the Group I, II or III metal on the periodic table is an amount of 0.05 to 5.0 parts by weight per 100 parts by weight of the thermoplastic polyester resin.

When less than 0.05 parts by weight of the compound is used, the effect of making the cell of the resulting foam fine and the compound containing two or more acid anhydride groups may not be sufficient to enhance the viscoelasticity, while the foam is used when the amount is more than 5 parts by weight. Is colored, and the viscosity of a fused thermoplastic polyester resin does not become high enough.

In the thermoplastic polyester resin foam production method of the present invention, any blowing agent which can be easily evaporated may be used.

Preference is given to foaming agents which are prone to evaporation, such as inert gases, saturated fatty acid hydrocarbons, saturated aliphatic ring hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers and ketones.

Examples of easily evaporating blowing agents include carbon dioxide, nitrogen, methane, ethane, propane, butane, pentane, hexane, methylpentane, dimethylbutane, methylcyclopropane, cyclopentane, cyclohexane, methylcyclopentane, ethylcyclobutane, 1,1 , 2-trimethyl cyclopropane, trichloro monofluoromethane, dichlorodifluoro methane, trichloro trifluoro ethane, dichloro tetrafluoro ethane, dichloro trifluoro ethane, monochlorodifluoro ethane, tetrafluoro ethane , Dimethylethyl-2-ethoxyethane, acetone, methyl ethyl ketone, acetyl acetone, dichloro tetrafluoro ethane, monochlorotetrafluoro ethane, dichloromono fluoroethane, difluoronoethane and the like.

Typically, the blowing agent is sprayed onto a molten mixture of thermoplastic polyester resins, and the compound and additives having two or more acid anhydride groups per molecule are sprayed into the extrusion process.

The amount of blowing agent to be sprayed is 0.05 to 50% by weight based on the amount of the molten mixture.

When the amount of the blowing agent is less than 0.05% by weight, the resulting foam is not sufficiently expanded, whereas when the amount of the blowing agent is 50% by weight or more, the gas of the blowing agent is not harmonized by the formation, and it is blown away to form the foam of the desired size.

The preferred amount of blowing agent is preferably 0.01 to 30% by weight based on the amount of the molten mixture.

In the method for producing a thermoplastic polyester resin presenter of the present invention, a stabilizer, an expansion nucleating agent, a pigment, a filler, a combustion sustaining agent, and an antistatic agent are optionally added to the resin mixture in order to improve the physical properties of the thermoplastic polyester resin foam. Can be molded.

In the method for producing the thermoplastic polyester resin foam of the present invention, molding may be performed by any blow molding process and extrusion process using a single screw extruder multiple screw extruder and a tandem extruder.

Dies used in the extrusion process or blow process are planar dies, rotary dies and nozzle dies, depending on the shape of the desired foam.

In the polyester resin of the present invention, a compound containing two or more acid anhydride groups per molecule and other additives are mixed by the following method.

(A) Compounds containing at least two acid anhydride groups per molecule in the thermoplastic polyester resin are compounded at low temperature (e.g., 150 or less) (e.g., powders of compounds containing at least two acid anhydride groups per molecule are thermoplastic polyester) Stick to the pellet surface of the resin).

(B) The compound containing two or more acid anhydride groups per molecule pelletizes the mixture which melt-mixed a thermoplastic resin previously, and mixes the pellet with a thermoplastic polyester resin.

(The thermoplastic resin may be the same as or different from the thermoplastic polyester resin, but a compound compatible with the thermoplastic polyester resin is suitable.)

(C) A thermoplastic polyester resin is supplied to the extruder hopper in advance and melted, and a compound containing two or more acid anhydride groups per molecule is supplied through a main inlet installed in the cylinder of the extruder to exhibit a mixing effect.

In any of the above-described mixing methods, the smaller the water content of the resin mixture is, the better it is, and it is preferable to reduce it to 200 PPM or less.

It is preferable to dry the thermoplastic polyester-based resin at 60-180 ° C. for 4 hours in a dehumidifying hot air dryer using hot air having a dew point of -20 ° C. or lower.

The present invention also relates to a method for producing a thermoplastic polyester resin foam, wherein immediately after expansion, the high temperature thermoplastic polyester resin foam is cooled to a temperature below the glass transition point of the resin to bring the crystallinity to 30% or less, and then the foam is heated to 60 ° C. or more. It is made to process. The preexpanded (primary expanded) foam extruded through the extruder had a low expansion rate and high density.

The expansion rate depends on the shape of the foam, but is about five times when the extruded foam is a sheet.

In the present invention, the pre-expanded foam obtained by the above production method has a high temperature after extrusion, but is cooled only to a temperature below the free point of the polyester resin.

The glass transition point of the polyester resin varies depending on the kind of carboxylic acid and alcohol constituting the polyester, but is generally in the range of 30-90 ° C.

Thus, the foams are generally cooled to temperatures up to 60 ° C. When the pre-expanded foam cools, its crystallinity is low because it hardens without time for crystallization to take place.

The crystallinity changes with the degree of cooling.

For example, the crystallinity depends on the type, the cooling medium and the temperature, and the contact conditions of the cooling medium and the foam.

When the pre-expanded foam produced by the extruder is in direct contact with water at room temperature, the crystallinity is within a few%-about 10%, and generally within 30%. Then, when forming the pre-expanded foam produced by extrusion, the crystallinity becomes 30% or more because the foam is not cooled unless the molding machine is forcibly cooled.

In particular, as the thick film crystallinity of the pre-expanded foam becomes 30% or more, cooling is given to the foam in which the pre-expanded foam is to be produced by the extruder.

In order to effectively perform cooling of the pre-expanded foam, the foam is preferably fertilized with its own volume to have a large surface area.

That is, the foam is preferably in the form of a sheet, the thickness of which should be within 10 mm, and preferably within 3 mm.

When the sheet is cylindrical, a mandrel is installed in the cylinder, the sheet runs in the direction of the water cooled mandrel and the length of the mandrel need not be as long as possible.

On the other hand, when the sheet is flat, it is necessary to sandwich the sheet between a pair of rollers, and while advancing while cooling, make the diameter of the rollers as long as possible.

In this way, the crystallinity of the pre-expanded foam is within 30%.

The foam is then reheated to effect post expansion (secondary expansion). The post expansion temperature of the foam is at least 60 ° C., and heating means can be used, for example in contact with a heating plate to carry out the heating.

At this time, the heating may alternatively be carried out from radiation, reflux, or high frequency force, and any heating medium adopted is not modified as long as the polyester resin is used as the medium.

Suitable heating methods are those in which the pre-expanded foam is brought into contact with a heating plate or air or with steam or hot water.

The heating time for post-expansion depends on the nature, form, type of resin and the temperature of the heating medium.

In general, the heating time is extended when the temperature of the heating medium is low, while the heating time is shortened when the temperature is high. In other words, the thick film heating time of the foam is extended and the thin film heating time of the foam is shortened. When feeding the foam into the metal, it is preferable to heat the metal plate to 60-200 ° C. to supply the pre-expanded foam and to contact the metal plate for about 5 minutes.

When heating the pre-expanded foam by supplying contact with hot air, the foam is placed on an oven, the temperature of the oven is raised to 100-230 ° C., and the foam is heated for 10 seconds to 5 minutes.

When the foam is heated by a metal plate or hot air, the foam is left for at least 24 hours, usually three days after pre-expansion and no post-expansion immediately after pre-expansion.

On the other hand, when the pre-expanded foam is supplied to steam or hot water, the post-expansion is immediately performed after the pre-expansion, in this case the temperature of the steam or water is 60-125 ℃, the contact time is 10 seconds-5 minutes. Polyester resin foams can be supplied to steam or hot water by a variety of methods.

For example, as shown in FIG. 1, the water repellent 1 is soaked in the hot water 2. In FIG. 1, reference numeral 8 denotes a burner, and in another embodiment, as shown in FIG. 2, the metal gauge 3 is placed on a hot water surface, and steam 4 vaporized in hot water 2 and Contact.

In another embodiment, pressurized steam 4 is pasted into a container 9 containing foam 1 as shown in FIG.

When the foam is heated in contact with hot water or steam, it is preferable to place it in the molding machine and mold it in the desired shape.

When using a molding machine, hot water or steam is introduced into the molding machine and the foam is directly contacted with hot water or steam.

In the above-described operation, the polyester resin foam is heated in contact with hot water or steam to be heated at 60 ° C. or higher, so that the foam becomes a post-expanded foam having low density.

In general, post-expansion can be made easier to heat with hot water or steam than with air.

In addition, steam is more preferred than hot water.

When heating is performed with hot water or steam, the post-expansion rate is at least 1.3, but lower than the pre-expansion rate, and can be 4 or more.

In addition to the above description, as the expansion is made uniform, the post-expanded foam has fine, uniform cells. This results in a low density foam of good quality.

The low-expansion foam can be easily obtained by heating the pre-expanded foam, but the post-expanded foam can impart a crystallinity of at least 15%.

Foams having a crystallinity of at least 15% have excellent heat resistance in a heated atmosphere and can be used in heat resistant food containers and heat insulating materials. Furthermore, the melt viscosity die swelling ratio of the thermoplastic polyester resin is adjusted by the process of the present invention to produce a foam sheet.

The density of the extruded foam sheet of the thermoplastic polyester resin is preferably 0.7 g / cm 3 or less, particularly 0.5 g / cm 3 or less. If the density exceeds 0.7 g / cm 3, thermal insulation, light weight and cushioning properties are lost. In terms of thermoforming, an extruded foam sheet having a crystallinity of 20% or less and a molecular orientation of 4.5 or less in the foam surface direction has been found to be preferred.

After extrusion, the extruded foam sheet is thermally insulated, so it is difficult to reduce the crystallinity through thickness.

However, post-expansion thermoforming can be improved by lowering the molecular orientation ratio below a predetermined value.

Molecular orientation of the extruded foam sheet as viewed in the foam sheet surface direction can be adjusted to 4.5 or less by controlling expansion in the extrusion direction and the direction crossing the extrusion direction.

As a preferred manufacturing method in connection with the above, a method using a rotating die columnar mandrel is generally used. That is, the expansion in the extrusion direction can be controlled by the average flow rate ratio of the molded resin from the outlet gap of the rotary die to the winding speed in the extrusion direction, and the expansion in the transverse direction in the extrusion direction is the exit straight of the rotary die up to the outer diameter of the mandrel. It can be adjusted by expense (hereinafter referred to as blow-up).

The crystallinity was measured according to Japanese Industrial Standard (JIS) -K-71222 (Method of Transition Heat Measurement of Plastic Materials) from the heat of fusion by calorimetry and calorific value DSC (differential parking calorimeter). That is, the crystallinity was measured by the following formula.

Crystallinity was measured using a differential scanning calorimeter DSC 200 manufactured by Seiko Kogyo Co., Ltd. As the amount of heat of complete crystal melting of polyethylene terephthalate, 26.9 KJ / mol was used in the data handbook (by Baifukan Kogyo Co., Ltd.) at the time of stirring.

The molecular orientation ratio in the foam front direction is a ratio between the maximum values of the microwave strengths emitted from the foam sheet surface through the polarizer plate (manufactured by Kanji Paper Co., Ltd.).

In addition, by bonding the non-foamed film of the thermoplastic resin to at least one side of the extruded foam sheet of the thermoplastic polyester resin according to the present invention to obtain a red-filled sike, by placing the non-foamed sheet on the inner surface and thermoforming with a food container Food containers can be obtained.

Examples of the thermoplastic resin composed of a non-foaming film include thermoplastic polyester resins, liquid crystal polyester resins, polyolefin resins, polyamide resins, polyvinyl chloride resins, polyacrylonitrile resins, polyvinylidene chloride resins, and ethylene vinyl alcohol hybrid polymers. Can be mentioned.

The non-foamed film to be bonded may be composed of a single layer film or a multilayer film, and the non-foamed film may be bonded to both sides of the foam sheet. The thickness of the non-foamed film layer is 10-500 microns, and the sheet layer thickness of the expanded polyester resin is generally slightly thicker than 5 mm.

The thickness of the foam sheet layer is preferably about 2-500 times that of the non-foamed film layer.

The unfoamed film can be laminated to the foam sheet via a parallel extruder.

In detail, the thermoplastic polyester resin is fed to an extruder to thoroughly extrude the expandable polyester resin.

Separately explained, the non-expandable resin is thoroughly extruded by supplying the thermoplastic resin to another extruder. The resin was guided to the die to prepare a sheet in the size of the die. In another example, the resin extruded through each extruder is air-tossed on a separate die to prepare a foam sheet and a film, and then placed on each other and pressed with a roller to produce a laminated sheet.

As another example, the foamed sheet and the non-foamed sheet were prepared separately, and then wound in a roller. They are stacked together by passing them through a pair of rollers without sensing them. It is preferable to lower the roller temperature on one side of the foam sheet, for example, room temperature prevents the crystallization of the polyester resin.

On the other hand, in order to change the film surface of the roller on one side of a non-foaming film, it is preferable to maintain high temperature.

The laminated sheet was reheated and formed into a container. At this time, thermoforming was performed using a molding die.

The die may be composed of a male and female molding machine, but any one of the groups may be selected.

A die consisting of two molding machines was used to squeeze the laminated sheet between the two molding machines.

However, when one of the two molding machines is used, the air existing between the sheet and the molding machine is removed or compressed by pressing the sheet from the top.

The non-foamed film was arranged so that the film was positioned inside the container.

The heating temperature at which the sheet is molded into the container is determined according to the thermoplastic polyester resin composed of the foam sheet and the thermoplastic resin composed of the non-foamed film. The same thickness difference occurred as the expansion temperature of the foam sheet increased or decreased by the heating temperature. Moreover, the crystallinity of the foam sheet was accelerated with heating temperature and heating time.

Extruded foam sheets composed of thermoplastic polyester resins exhibit a crystallinity of at least 15%, which is very excellent in heat resistance when heated in bone. However, when exposed to heat steam of 100 DEG C or higher, the thickness of the film wall of the single cell on the surface is thin and the single layer cell is reshrunk.

In addition, when used for food containers required to heat foods such as soup and gratin, food liquid may penetrate the cell.

On the other hand, in the present invention, since the non-foamed film is located inside the container, it is possible to allow the liquid of the re-inflated food by steam or hot water to pass through the cell.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Test Examples, but the present invention is not limited thereto.

EXAMPLE

[Test Example 1]

Compounds having two or more acid anhydride groups per molecule during melting were added to the thermoplastic polyester crab resin to test the effect of viscoelastic properties.

(1) Test-1

Polyethylene terephthalate (PET9902 Eastman Co.) was dried at 160 ° C. for 4 hours in a dehumidifying dryer with hot air having a dew point of −30 ° C. 1 kg of dried material is mixed with 5 g of 2 anhydrous pyromellitic acid (available from Chemischer Birvewheels AC) and the mixture is equipped with a single screw extruder equipped with a cylindrical passage die (5 mm in diameter, L / P: 106). It supplied to the hopper ((Screw diameter: 40 mm, L / D: 30, Sekis Co., Ltd. make).

The supplied molten mixture was extruded through a cylindrical passage die at an extrusion rate of 7 kg / Hr under the following manufacturing conditions to carry out molding.

Condition by Single Scout Extruder

Extruder Feed Zone Temperature: 270 ℃

Extruder Press Zone Temperature: 280 ℃

Extruder Melting Zone Temperature: 270 ℃

Die temperature: 270 ℃

Speed of screw extruder: 32rpm

(2) test-(control)

Extrusion of polyethylene terephthalate was carried out in the same manner as in Test-1, except that the anhydrous pyromellitic acid mixture was omitted.

(3) Test result

In the single screw extruder, the melt viscosity of the molten resin and the die expansion rate of the extruded material are shown in the first table.

(1) Review

It can be seen from the first table that when dihydric anhydrous pyromellitic acid is added to polyethylene terephthalate, the die expansion ratio of the extruded material increases and the melt viscosity of the molten resin also increases in extrusion.

EXAMPLE

Example 1

Polyethylene terephthalate 10 was dried in a dehumidifying dryer (160 hot air with a dew point of -30) for 4 hours, and 20 g of anhydrous pyromellitic acid (available from Chemischer Bervewheels AC) in a tumbling mixer 60 g of expanded nucleating agent) were mixed.

The mixture was fed into a single screw extruder hopper (screw diameter: 40 mm, L / D: 30, hole in nozzle die: 5 mm), melt mixed, and 22% by weight of isopentane (foaming agent) was injected into the melt mixture. . The molten mixture was extruded into air through a nozzle die under the following manufacturing conditions to produce a rod-shaped foam.

Manufacturing Conditions by Single Screw Extruder

Extruder Feed Zone Temperature: 273-282 ℃

Extruder Press Zone Temperature: 280-290 ℃

Extruder Melting Zone Temperature: 271-290 ℃

Temperature of extruder head: 280-290 ℃

Speed of screw extruder: 32rpm

Extrusion Speed: 7-8kg / hr

Example 2

A rod-shaped foam was prepared by repeating the process of Example 1 except adding 30 g of anhydrous pyromellitic acid and spraying 2.5% by weight of isopentane into the melt mixture.

The expansion rate and the diameter of the foams are shown in the second table.

Example 3

40 g of 2Mellitic anhydride was added, and the process of Example 1 except having sprayed 2.6 weight% of isopentane to the melt mixture was repeated, and the rod-shaped foam was produced.

[Comparative Example]

Comparative Example 1

2 Effect of Anhydrous Pyromellitic Acid (1)

A rod-shaped foam was produced by repeating the process of Example 1 except that 2 anhydrous pyromellitic acid was removed and 2.7% by weight of isopentane was injected into the molten mixture.

The expansion rate and the diameter of the foam are shown in Table 2.

Comparative Example 2

Effect of pyromellitic anhydride (2)

A rod-type foam was obtained by repeating the process of Example 1 except that 50 g of phthalic anhydride was added instead of 2 g of anhydrous pyromellitic acid and 2.7 wt% of isopentane was injected into the molten mixture.

The expansion rate and the diameter of the foam are shown in Table 2.

Review

In Examples 1-3 using pyromellitic dianhydride, the expansion ratio is 4-10, and as the diameter of the rod-shaped foam increases to 4-6 times the size of the nozzle die, the resulting increase rate is injected isopentane. It can be seen from the second table that it is proportional to the increase in amount.

In Comparative Examples 1 and 2 excluding pyromellitic anhydride, the expansion ratio is about 2, and although the isopentane (foaming agent) is larger than the amount used in Examples 1-3, the diameter of the rod-shaped foam is determined by the hole of the nose die. It is about twice the size.

Therefore, the expansion rate and diameter are smaller than those in Examples 1-3.

If no anhydrous pyromellitic acid is used, the blowing agent isopentane is released from the blowing agent during expansion molding, whereas when 2 anhydrous pyromellitic acid is used for expansion molding, the melt viscosity of the thermoplastic polyester is increased, resulting in the This effect has been taken into account from the fact that pentane prevents from leaving the foam.

Example 4

In the process of Example 3, it was observed that there was no change in the rod-shaped foam as a result of continuous expansion molding operation for 24 hours.

Example 5

In Example 3, the inflation molding operation was performed for 5 hours and then left for 19 hours. Thereafter, a rod-shaped foam of colorlessness and high purity can be obtained within 30 minutes from the start of the operation.

Comparative Example 3

In Example 3, diglycidyl terephthalate (Blemer, Japanese Yushi Co., Ltd.) was used instead of dihydroan pyromellitic acid, and 4 g of isopentane per 100 g of the mixture was dispersed in the application mixture.

The operation was performed in the same manner as in Example 5.

In the process after the third process, it continued for 90 minutes or more until a colored foam or rod-shaped foam was obtained.

In the fifth process (presentator), after 4 hours from re-starting, the yellow coloration and black material was contaminated.

Example 6

A rod-shaped foam was prepared by repeating the process of Example 1 except that 50 g of cyclopentane tetracarboxylic dianhydride was used instead of 20 g of pyromellitic dianhydride. The expansion rate of the foam was 4 and the diameter was 20 mm.

Example 7

Foam was prepared by repeating the process of Example 1 except that 50 g of benzophenone tetracarboxylic dianhydride was used instead of 20 g of pyromellitic dianhydride. The expansion ratio of the foam was 4.5 and the diameter was 20 mm.

Example 8

In Examples 6 and 7, the operation was carried out as in Example 5.

Rod-like foams were obtained which did not complex or contaminate within 30 minutes from the start of the operation.

Example 9-17

The polyethylene terephthalate shown in Table 3 was dried at 60 ° C. for 4 hours in a hot air dehumidifying dryer having a dew point of −30 ° C.

100 parts by weight of dried polyethylene terephthalate, the amount of dihydroan pyromellitic acid shown in Table 3, the metal compound shown in Table 3 and 0.6 parts by weight of talc (expansive nucleating agent) were mixed in a tumbling mixer. This mixture was sprayed onto the molten mixture with 2.0 parts by weight of n-pentane equipped with a nozzle die (hole: 5 mm). The molten mixture was extruded under the following conditions to prepare rod-shaped foams.

Extruder Feed Zone Temperature: 268-280 ℃

Extruder Press Zone Temperature: 285-290 ℃

Extruder Melt Zone Temperature: 275-285 ℃

Extruder Head Temperature: 275-285 ℃

Screw Speed: 32rpm

The expansion rate of the foam and the state of the cells are shown in Table 3.

8 is an electron micrograph at 25 times magnification of the cell state of the foam prepared in Example 9. FIG.

As shown in Figure 8, the cell is small.

9 and 10 are electron micrographs at 25 times magnification of the cell state of the foams produced in Examples 12-17, respectively.

The cell of the foam prepared in Example 17 was slightly enlarged than that produced in Example 12.

[Comparative Example 4]

A rod-shaped foam was prepared by repeating the process of Example 9, except that 2 anhydrous pyromellitic acid and a metal compound were removed.

The expansion rate and cell state of the foams are shown in Table 3.

Example 18-20

Except for using the polyester resin, acid anhydride and metal compound shown in Table 4, the process of Example 9 was repeated to prepare a foam.

[Comparative Example 5]

Foams were prepared in the process of Example 9, except that the polyethylene terephthalate and diglycyl terelate shown in FIG. 4 were used without using a metal compound.

The expansion rate and cell state of the foams are shown in Table 4.

Example 21

The polyethylene terephthalate shown in Table 5 was dried for 4 hours at 160 ° C. in a dehumidifier dryer with hot air having a dew point of −30 ° C.

100 parts by weight of dried polyethylene terephthalate, 0.5 parts by weight of dihydroan pyromellitic acid, 0.1 parts by weight of sodium carbonate and 0.6 parts by weight of talc (expanded nucleating agent) were mixed in a tumbling mixer.

The mixture was fed into a columnar mandrel (hole: 205 mm, L / D: 35), and 1.7 parts by weight of butane was injected into the molten mixture.

The melt mixture was extruded through a rotary die under the following conditions. The extrudate was molded into a cylindrical mandrel.

The cylindrical foam was cut open and the resulting foam sheet was wound.

Extruder Feed Zone Temperature: 280 ℃

Extruder Press Zone Temperature: 290 ℃

Extruder Melt Zone Temperature: 280 ℃

Extruder head temperature: 280 ℃

Injection pressure of blowing agent: 80kg / hr

Screw Speed: 32 ℃

Extrusion Speed: 24kg / hr

Table 5 shows the tensile calculations when the foamed sheet at 23 ° C. was subjected to dissipation rate, cell state, tensile strength, and tension at 23 ° C.

Comparative Example 6

The foam sheet prepared by repeating the process of Example 21 was wound except that diglycidyl terephthalate and sodium montanate shown in Table 5 were not used.

The expansion rate, cell state, tensile strength of the foam sheet at 23 ° C., and stable elongation at tension at 23 ° C. are shown in Table 5.

Comparative Example 7

The diglycidyl terephthalate shown in Table 5 was soluble, sprayed with 0.9% by weight of butane, extruded under the following conditions and produced by the process of Example 21 except that sodium carbonate was not used. The foam sheet was wound.

Extruder Feed Zone Temperature: 280 ℃

Extruder Press Zone Temperature: 290 ℃

Extruder Melt Zone Temperature: 280 ℃

Extruder head temperature: 285 ℃

Extruder Die Temperature: 275 ℃

Injection pressure of blowing agent: 40kg / ㎠

Extrusion Pressure (Head): 90kg / ㎠

Screw Speed: 25rpm

Extrusion speed: 24kg / h

Table 5 shows the tensile elongation at the time of extrusion of the foam sheet at 23 ° C., the cell state, the tensile strength and the tension at 23 ° C.

PET 9902 and PET 10388: products from Eastman Kodak

TR 4550 BH and TR 8510: Daichinsa Products

Sodium Carbonate: product from Tosoh Corporation

2 Anhydrous pyromellitic acid: manufactured by Chemischerveil Wheels AG

TR 8580: Daichinsa Products

XD 478 (MI: 3.0, 235 ℃) For polybutylene telephthalate: Plastics

2 anhydrous pyromellitic acid: manufactured by Hicks Japan

Sodium Carbonate: product from Tosoh Corporation

PET 9902 and PET 10388: products from Eastman Kodak

TR 8580: Daichinsa Products

2 Anhydrous pyromellitic acid: manufactured by Chemie Verve Wheels AG

Diglycidyl terephthalate: Blamer DGT from Nippon Yushi

Sodium Carbonate: product from Tosoh Corporation

Experimental Example 2

Test sample: Foam sheet prepared in Example 21 and Comparative Example 6

Test Method: Using a dynamic viscoelastic polymer (manufactured by Toyosei Seishi Corporation)

The composite elastic modulus of the test sample (5 mm (width) x 21 mm (length) x 1.5 mm (thickness)) was measured under the following conditions.

Measuring frequency: 10Hz

Heating rate: 3 ℃ / min

Distance between clamps: 15mm

The results are shown in FIG.

The composite elastic modulus of the foam sheet of Example 21 was higher than that of the foam sheet of Comparative Example 6.

Therefore, it can be seen that the heat resistance of the foamed sheet produced by using the anhydrous pyromellitate and sodium carbonate is high.

The method of manufacturing a thermoplastic polyester resin by reheating was demonstrated by the method of the following Example and a comparative example.

Unless otherwise specified, parts and percentages refer to parts by weight and percentages by weight.

Example 22

Total expansion (primary expansion):

TR 8580 (trade name, manufactured by Daichin Inc.) was used as polyethylene terephthalate (hereinafter referred to as PET).

The PET was placed in a dehumidifier and dried at 160 ° C. for 4 hours while circulating hot air with a dew point of −30 ° C.

100 parts of PET, 0.6 parts of talc, 0.35 parts of 2 anhydrous pyromellitic acid and 0.1 parts of sodium carbonate were mixed thoroughly in a tumbling mixer.

The mixture was fed to a compressor (screw diameter: 65 mm, L / D: 35) and mixed at 25 rpm screw speed at a barrel temperature of 270-290 ° C.

1.3 parts of butane per 100 parts of the mixture were introduced into the mixture while pressurized into the barrel chamber as a blowing agent, and the PET including the blowing agent was extruded into the air through a rotary die to prepare a tube.

A die with a rotating die gap of 0.4 mm and a hole of 60 mm was maintained at 270-285 ° C., introduced into and contacted with the outer surface of the cylindrical mandrel to expand the extruded PET into the air, and the extruded tube was taken out.

Cooling water at 30 ° C. was circulated to quench the PET foam inside the mandrel with an outer diameter of 205 mm.

The cooled PET foam was cut at the outlet and the flat foam sheet wound up was wound up.

The above relates to preexpanded foam sheets (primary expanded foam sheets). The foam sheet had a width of 643 m, an apparent density (hereinafter referred to as density) of 0.26 g / kg, a thickness of 1.5 mm, and a crystallinity of 9%.

Post-expansion (secondary expansion)

One sample obtained by cutting the pre-expanded foam sheet to a size of 100 mm x 100 mm was applied to the post-expansion.

As shown in FIG. 1, the sample was added to hot water at 63 ° C. and post-expansion was performed for 5 minutes. The thickness of the resulting one was expanded to 1.5 x 2.1 mm.

The volume ratio V / V of the post-expanded foam sheet to the volume (V) of the pre-expanded foam sheet was 1.37.

The density of the post-expanded foam sheet is 0.19 g / cm The crystallinity was 9%.

The post-expanded foam sheet was found to be a good foam with good expansion.

Example 23

Post-expansion was carried out by the method of Example 22 using the same pre-expanded foam sheet prepared in Example 22, except that it was immersed in warm water at 83 ° C for 5 minutes.

In this way, a thickness of 3.02 mm, 0.13 g / cm A post-expanded foam sheet having a density of 10%, a crystallinity of 10% and a V / V ratio of 2.00 was obtained.

Fine, uniformly expanded foam sheets were found to be excellent foams with low density.

Example 24

FIG. 2 shows that the same pre-expanded foam sheet as obtained in Example 22 was subjected to post-expansion by contact with steam.

That is, the sheet was contacted with steam at 62 ° C. for post-expansion for 5 minutes.

In this way, a thickness of 2.51 mm, 0.16 g / cm A post-expanded foam sheet having a density and a V / V ratio of 1.63 was obtained.

Example 25

The same procedure as in Example 24 was carried out except that steam at 75 ° C. was applied to the post-expansion.

In this way, a thickness of 2.73 mm, 0.14 g / cm A post-expanded foam sheet having a density and a V / V ratio of 1.86 was obtained.

Example 26

Post-expansion was carried out in the same manner as in Example 24, except that steam and contact time at 100 ° C. were 5 minutes.

In this way, a thickness of 2.78 mm, 0.14 g / cm Density, 10% crystallinity and V

A post-expanded foam sheet having a / V ratio of 1.86 was obtained.

Example 27

As shown in FIG. 2, the same procedure as in Example 26 was carried out except that the sheet was contacted with steam at 100 ° C. for post-expansion for 2 minutes.

In this way, a thickness of 3.92 mm, 0.10 g / cm A post expansion foam sheet having a density of 16%, a crystallinity of 16% and a V / V ratio of 2.60 was obtained.

Example 28

The same procedure as in Example 26 was carried out except that the sheet was supplied to and contacted with steam at 100 ° C. and then subjected to post-expansion for 5 minutes.

In this way, a thickness of 5.63 mm, 0.065 g / cm A post-expanded foam sheet having a density of 26%, a crystallinity of 26% and a V / V ratio of 3.77 was obtained.

Example 29

Example 26 was carried out except that post-expansion was performed for 7 minutes by contacting the sheet with steam at 100 ° C.

In this way, a thickness of 5.96 mm, 0.065 g / cm A post-expanded foam sheet having a density of 4 and a V / V ratio of 4.00 was obtained.

Example 30

Post-expansion was carried out in the same manner as in Example 29 for 7 minutes by placing the sheet in contact with steam at 100 ° C. except that the pre-expanded foam of 200 mm to 280 mm was placed in a 210 mm to 290 mm to 5 aluminum molded body. Was carried out.

In this way, a thickness of 5.00 mm, 0.078 g / cm An expanded sheet having a density and a V / V ratio of 3.33 was obtained.

The sheet is a flat foam sheet.

Example 31

The same pre-expanded foam sheet as in the sheet obtained in Example 22 was blown with pressurized steam to post-expand as shown in FIG.

That is, the sheet was contacted with steam at 110 ° C. for post-expansion for 3 minutes.

In this way, a thickness of 3.41 mm, 0.11 g / cm The post-expansion sheet whose density and V / V ratio were 2.36 was obtained.

Example 32

As in Example 31, except that the sheet was contacted with steam at 120 ° C. for post-expansion for 5 minutes.

In this way, a post-expansion sheet having a thickness of 3.00 mm, a density of 0.13 g / cm 3 and a V / V ratio of 2.00 was obtained.

Example 33

Pre-expansion was carried out in the same manner as in Example 22, except that 1.1 parts of carbon dioxide was used as a blowing agent instead of butane.

This gave a pre-expansion sheet having a width of 643 mm, a density of 0.26 g / cm 3, a thickness of 1.5 mm and a crystallinity of 9%.

As a result of post-expansion in the same manner as in Example 28, a post-expansion sheet having a thickness of 3.00 mm, a density of 0.13 g / cm 3 and a V / V ratio of 2.60 was obtained.

Example 34

The same procedure as in Example 22 was carried out except that the sheet was contacted with hot air at 80 ° C. instead of 63 ° C. hot water for 5 minutes, and then expanded to a thickness of 2.1 mm, a density of 0.19 g / cm 3, and 10%. The post-expansion sheet whose crystallinity and V / V ratio were 1.37 was obtained.

Example 35

In Example 34, the post-expanded foam sheet was obtained in the same manner as in Example 34 except that the hot air temperature in water expansion was set to 100 ° C.

The post-expanded foam sheet had a thickness of 2.6 mm, a density of 0.15 g / cm 3, a crystallinity of 10%, and a V / V ratio of 1.37.

Example 36

In Example 34, the post-expanded foam sheet was obtained in the same manner as in Example 34 except that the hot air temperature in water expansion was set at 110 ° C.

The post-expanded foam sheet had a thickness of 2.8 mm, a density of 0.14 g / cm 3, a crystallinity of 12%, and a V / V ratio of 1.86.

Example 37

In Example 34, the expanded sheet was expanded in the same manner as in Example 34 except that the hot air temperature in the post-expansion was 140 ° C.

The post-expanded foam sheet had a thickness of 3.01 mm, a density of 0.13 g / cm 3, a crystallinity of 25%, and a V / V ratio of 2.00.

Example 38

In Example 34, the post-expanded foam sheet was obtained in the same manner as in Example 34 except that the hot air temperature in the post-expansion was 23 ° C.

The post-expanded foam sheet had a thickness of 4.04 mm, a density of 0.097 g / cm 3, a crystallinity of 26%, and a V / V ratio of 2.68.

Example 39

Pre-expansion:

The die prepared in the extruder head was changed from a rotary die to a flat die, and pre-expanded in the same manner as in Example 22 except that a flat plate was used instead of a mandrel. This flat die had a linear extrusion port having a width of 150 mm and a width of 0.7 mm. The plate was an aluminum plate of 500-500 mm cooled with water at 30 ° C. The foam sheet was extruded between aluminum plates, and the extruded foam sheet was cooled. In this manner, the foam sheet was pre-expanded.

The foam sheet had a width of 200 mm, a thickness of 5 mm, a density of 0.52 g / cm 3, and a crystallinity of 12%.

Post-expansion:

The pre-expanded foam sheet was brought into contact with steam at 100 ° C. for 7 minutes to be post-expanded in the same manner as in Example 29. This gave a post-expanded foam sheet having a thickness of 12.5 mm and a density of 0.204 g / cm 3 with a V / V ratio of 2.55.

Example 40

In Example 39, the expanded sheet was pre-expanded in the same manner as in Example 39 except that the temperature of the aluminum plate was slightly warmed, and the foam sheet was cooled slightly smaller than in Example 39.

The width, thickness and density of this foam sheet were similar to that of the sheet of Example 39. However, the crystallinity was 25%.

Post-expansion:

Post-expansion was carried out in the same manner as in Example 39 to obtain a post-expansion foam sheet having a thickness of 11.0 mm and a density of 0.232 g / cm 3, with a V / V ratio of 2.44.

Comparative Example 8

In Example 22, 60 degreeC hot air was used instead of 63 degreeC warm water, and the sheet was post-expanded in the same manner as in Example 22 except that the sheet was brought into contact with hot air for 5 minutes to obtain a post-expanded foam sheet.

The post-expanded foam sheet had a thickness of 1.5 mm, a density of 0.26 g / cm 3, and a V / V ratio of 1.00 as in Fertilizer Example 8. Therefore, substantially no post-expansion occurred.

Comparative Example 9

In Example 22, the foam sheet which was post-expanded was obtained in the same manner as in Example 2 except that the water temperature at the time of post-expansion was lowered to 53 ° C.

The thickness of this post-expanded foam sheet was 1.5 mm, the density was 0.26 g / cm 3, and the V / V ratio was 1.00 as in Comparative Example 8. Therefore, substantially no post-expansion occurred.

Comparative Example 10

In Example 24, the foam sheet which was post-expanded was obtained in the same manner as in Example 24 except that the temperature of the steam at the time of post-expansion was lowered to 58 ° C.

The post-expanded foam sheet had a thickness of 1.5 mm and a density of 0.26 g / cm 3 with a V / V ratio of 1.00. Therefore, substantially no post-expansion occurred.

Comparative Example 11

The temperature of the aluminum plate was lowered than in Example 40, the cooling of the extruded sheet was made narrower in Example 40, and post-expanded in the same manner as in Example 40 to obtain a post-expanded foam sheet. The width, thickness and density of this foam sheet were the same as those of the foam sheet of Example 40, but the crystallinity was 32%.

The post-expanded foam sheet was post-expanded by contacting steam at 100 ° C. for 7 minutes to obtain a post-expanded foam sheet having a thickness of 5 mm and a density of 0.52 g / cm 3. The V / V ratio was 2.00. Therefore, substantially no post-expansion occurred.

Example 41

As shown in FIG. 4, pre-expansion and post-expansion were continued. In FIG. 4, the extruder 5 was operated in the same manner as in the rear window of Example 22, and the post-expanded foam sheet was continuously sent out.

The post-expanded foam sheet was not sensed and placed in the steam tank 6 continuously. The sheet surface temperature was lowered to 30 ° C. before entering into the steam tank 6. In FIG. 4, reference numeral 10 denotes a winding machine.

The pre-expanded foam sheet was post-expanded by contacting steam at 100 ° C. for 5 minutes in the steam tank 6.

The sheet was then cooled.

The resulting post-expanded foam sheet was 645 mm wide, density 0.07 g / cm 3, thickness 5.5 mm, low density microsheet expanded with high expansion rate and had fine and uniform cells.

Example 42

100 parts of polyethylene terephthalate pellets (trade name TR 8580 manufactured by Dichinchin) were dried at 160 ° C. for 5 hours with hot air having a dew point of −20 ° C. 0.3 parts of anhydrous pyromellitic anhydride, 0.1 parts of sodium carbonate, and 0.6 parts of talc as expansion nucleating agent were uniformly mixed with the pellets in a tumbling mixer.

This mixture was fed to the hopper of an extruder (screw diameter: 65 mm, L / D: 35).

The cylinder temperature was 265-290 degreeC, the extruder head temperature was 265 degreeC, die temperature was 265 degreeC, and the screw speed was 25 rpm. While applying pressure to the cylinder chamber, 2.4% butane was added as a blowing agent.

The die used was a rotating die with a diameter of 60 mm and a die gap of 0.45 mm. The tube was extruded through the die, and the molten resin was expanded and simultaneously melted in a columnar shape with a columnar mandrel device.

The resulting columnar foam part was opened and the sheet obtained was wound up. At this time, the surface temperature was maintained at 20 ° C while circulating the cooling water in the columnar mandrel.

The resulting foam sheet had a density (D) of 1.225 g / cm 3, width of 640 mm and thickness of 2.6 mm. The sheet had a crystallinity of 9.7% and a glass transition temperature of 75 ° C.

The sheet was reheated by heating and contacting the sheet for 30 seconds using a heating plate having a surface temperature of 160 ° C.

Thus, a post-expanded foam sheet having a density (D) of 0.133 g / cm 3 and a thickness of 2.7 mm was obtained. The ratio of D / D by heat treatment was 1.69. The crystallinity of the sheet was 24.3%. 100 * 100mm was cut out from the sheet | seat, and it heated at 200 degreeC for 30 minutes in the thermostat. The ratio Va / Vb of the volume Va after heating to the volume Vb before heating was 1.02.

It was found that this sheet was excellent in heat resistance.

Example 43

100 parts of polyethylene terephthalate pellets (trade name PET 10388, product of Eastman Kodak) were dried at 160 ° C with hot air at dew point -20 ° C.

0.25 parts of diglycidyl terephthalate (Blemer DGT, Nippon Yushi Co., Ltd.), 0.1 moles of sodium montanate and 0.6 parts of talc as an expanding nucleating agent were mixed uniformly in a tumbling mixer.

The mixture was fed to the hopper of an extruder as used in Example 42.

The cylinder temperature was 28 390 ° C., the extruder head temperature was 290 ° C., the die temperature was 290 ° C., and the screw rotation speed was 25 rpm. 2.2% of pentane as a blowing agent was pressurized to the mixture of the cylinder chamber.

The resulting foam sheet had a density (D) of 2.242 g / cm 3, a width of 640 mm, and a thickness of 17 mm. The crystallinity of the sheet was 10.6% and the glass transition temperature was 76 ° C.

The sheet was reheated by contact heating of the sheet for 30 seconds using a heating plate having a surface temperature of 160 ° C. The resulting sheet had a density D of 0.147 g / cm 3 and a thickness of 2.8 mm. The ratio of D / D by heat treatment was 1.65.

The crystallinity of the post-expanded foam sheet was 24.4%.

A 100 × 100 mm sample was removed from the site and heated at 200 ° C. for 30 minutes in a thermostat.

The ratio of V / V was 1.02.

Example 44

The extruded foamed site obtained in Example 42 was heated in contact with a heated plate having a surface temperature of 170 ° C. for 6 seconds to obtain a foam sheet having a density (D) of 0.106 g / cm 3 and a thickness of 3.4 mm. The crystallinity of the post-expanded foam sheet was 16.7%.

The sample 100x100m was cut out from the sheet | seat, and it heated at 200 degreeC for 30 minutes in the thermostat.

The ratio of Va / Vb was 1.06.

Example 45

The extruded foam sheet obtained in Example 42 was heated with steam at 4 atmospheres of steam for 30 seconds to obtain a foam sheet having a density (V) of 0.157 g / cm 3 and a thickness of 2.3 mm.

The ratio of D / D by this heating was 1.43.

The crystallinity of the post-expanded foam sheet was 24.3%.

The sample 100x100 mm was cut out from the sheet | seat, and it heated at 200 degreeC for 30 minutes in the thermostat.

Comparative Example 12

A sample 100 × 100 mm was cut out from the foam sheet extruded in Example 42. The crystallinity was 9.7%.

This sample was heated to 200 degreeC for 30 minutes in the thermostat.

Va / Vb was 1.74. There was no heat treatment after extrusion. The sheet thus obtained was poor in heat resistance and severely deformed.

Comparative Example 13

The extruded foam sheet obtained in Example 42 was heated for 10 seconds using a heating plate having a surface temperature of 140 ° C. to obtain a post-expanded foam sheet. The crystallinity was 131.5. The sheet density was 0.14 g / cm 3 and the thickness was 3.15 mm. The ratio of D / D by heating was 1.97.

The sample 100x100 mm was cut out from the sheet | seat, and it heated at 200 degreeC for 30 minutes in the thermostat.

Va / Vb was 1.11.

The results of Examples 42 to 45 and Comparative Examples 12 and 13 are shown in FIGS. 6 and 7.

MD: Extrusion direction of foam sheet

TD: perpendicular to MD

As is apparent from Tables 6 and 7, the volume of the unheated sheet changed considerably and the heat resistance of the sheet was poor.

In addition, when the sheet was heat-treated, the sheet having a crystallinity of less than 15% had poor heat resistance.

The following Examples 46-49 and Comparative Examples 14-16 show the extrusion foam sheet of thermoplastic polyester resin and its thermoforming.

[Examples 46-49 and Comparative Examples 14-16]

The production apparatus for the extruded foam sheet used in this example and the comparative example was a single screw extruder (screw diameter: 65 mm, L / D: 35).

The extrusion die was a rotating die (bore: 60 mm), and the rotating die gap of the extrusion die was deformed as in the ninth table.

The columnar mandrel was a water-cooled mandrel (outer diameter: 205 mm, L / D: 1.5).

As for the composition of the extruded foam sheet used in this example and the comparative example, 100 parts by weight of polyethylene terephthalate (PET) was used as the thermoplastic polyester resin.

The resin grade was changed as in Table 8.

0.6 parts by weight of talc was used as the expansion nucleating agent based on 100 parts by weight of PET.

Liquefied butane was used as the blowing agent in the amounts shown in Table 8.

The extruded foam sheets used in Examples 46 to 49 and Comparative Examples 14 to 16 were produced by the following operations.

Polyethylene terephthalate was dried for 4 hours in a dehumidifying dryer (160 ° C, dew point -30 ° C).

This polyethylene terephthalate, a modifier, a metal compound, and a predetermined amount of talc were mixed in a tumbling mixer.

The mixture was fed to an extrusion hopper and melt mixed.

Liquefied butane was injected into the mixture of the extrusion chamber as a blowing agent.

This mixture was extruded into the air through a rotating mirror of a rotating die to create a tubular shape.

The extrudate was taken out while expanding the molten resin, brought into contact with the outer surface of the columnar mandrel, and cooled to a columnar shape.

The columnar foam was taken out and the foam sheet was wound up.

The production conditions of the extruded foam sheet used in this example and the comparative example were as follows.

Extruder Feed Zone Temperature: 275-285 ℃

Extruder compression zone temperature: 285-295 ℃

Extruder Melt Zone Temperature: 265-285 ℃

Extruder head temperature: 265-285 ℃

Rotary Die Temperature: 260-285 ℃

Injection pressure of blowing agent: 40-140kg / ㎠

Extrusion Pressure: 50-120kg / ㎠

The rotation speed and the winding speed of the screw are shown in Table 9.

The resulting foam sheet had a width of 640 to 643 mm.

Apparent viscosity, thickness, crystallinity and molecular orientation are as shown in Table 10.

The post thermoforming machine and thermoforming conditions of the extruded foam sheet used for measurement in the examples and comparative examples of the present invention were as follows.

The post-heat molding machine was a single-shot machine for expanded polystyrene and had a heating zone of infrared radiation and a compression section of an air cylinder.

The molding apparatus was a flag-assist press tool (inner diameter: 180 mm x 155, depth: 95 mm) for container molding.

The molding conditions were that the 360 x 360 mm foam sheet was heated at 175 ° C for 15 seconds in a heating zone, and then contacted with the molding machine for 25 seconds to obtain the effect of molding.

The following items were measured about the produced molding.

(Exterior)

(Circle): The whole sheet was extended uniformly, was formed in the same shape as a crimping | compression-bonding mechanism, and was not damaged.

(Triangle | delta): Although it shape | molded in the same shape as a crimping mechanism, a surface part is damaged and it generate | occur | produces uniformly.

X: The sheet was badly damaged and molding was impossible.

(Thickness ratio)

Refers to the ratio of the thickness of the bottom to the sidewall of the molding.

The-mark means that the molding is badly damaged and cannot be measured.

(Surface)

(Circle): The surface of a molded object is smooth.

(Triangle | delta): The surface of a molding is partially uneven.

X: The surface of the molding is very uneven.

(General comment)

The surface and post-heat moldings of the extruded foam sheet were generally considered in consideration of both appearance and thickness.

◎: very good

○: excellent

×: inferior

The results are shown in Table 11.

Molecular orientation can be controlled by group speed and blow-up ratio, because the sheet is oriented in the MD direction when the winding speed is increased, while the blow-up ratio is increased (the cooling mandrel diameter is Increasing), the sheet is oriented in the TD direction.

However, when the width, thickness, and expansion rate of the sheet are fixed, the molecular orientation rate cannot be adjusted only by adjusting the winding speed and blow up ratio.

In this case, the die temperature increases (Example 47, Comparative Example 15).

The molecular orientation can be lowered by reducing the amount of melt modifier (Example 47, Comparative Example 14).

The crystallinity can be lowered by lowering the cooling water temperature to the columnar mandrel.

In addition, the food container of the present invention will be illustrated in the following Examples and Comparative Examples.

Unless otherwise specified, it means parts by weight.

Example 50

Here, the same thermoplastic polyester resin was used for the foamed sheet and the non-foamed sheet.

100 parts of polyethylene terephthalate pellets (trade name: TR 8580, manufactured by Daichin Corporation) were used as the polyester resin, and dried at 160 ° C for 5 hours with hot air at a dew point of -20 ° C.

0.3 part of 2 anhydrous melic acid, 0.1 part of sodium carbonate, and 0.6 part of talc were added there.

This mixture was mixed uniformly in a tumbling mixer and then fed to the extruder.

The cylinder temperature of the extruder was operated at 274-287 degreeC, and die temperature was 277 degreeC.

About 1.0 weight% of butane was pressurized and supplied to the compound of the cylinder seal as a blowing agent.

A die having a rotating cylinder was installed in the extruder head.

The polyester resin containing butane was extruded cylindrically through a rotary gap.

The extrudate was applied to a cylindrical mandrel while expanding the resin to obtain a foam sheet. The columnar foam sheet was opened and the resulting flat sheet was rolled into the mold. The resulting foam sheet had a density of 0.262 g / cm 3, a thickness of 1.45 mm, and a width of 640 mm.

A polyethylene terephthalate resin film (FFL Daichin Corporation) having a thickness of 50 µ was used as the non-foamed thermoplastic resin film. The film and the sheet described above were sandwiched between a pair of rollers. The roller temperature of the foam sheet width was room temperature, while the roller temperature of the non-foamed sheet width was operated at 135 ° C. In this way, the laminated site in which the non-foamed sheet was bonded only to one side of the foam sheet was obtained.

The sample of 250x250 mm was cut out from this laminated sheet, and it preheated by making it contact with the heating plate of surface temperature 140 degreeC for 6 second. Subsequently, the preheated sample was left for 6 seconds between the preheated at 180 ° C. and the female preheated at 180 ° C. to form a container and to accelerate the crystallinity. Immediately thereafter, the moldings were cooled by placing them between the sudie and the arm die for 6 seconds at room temperature, which also had the same shape as those of the white die preheated to 180 ° C. The non-foamed film layer was molded in such a manner as to be located inside the container. The shape of the obtained container is as shown in FIG. 6 and FIG.

FIG. 6 is a side view of the container 7 obtained, and FIG. 7 is a plan view of the container 7. In the isoform, the composite sheet had an increased expansion ratio, and the bottom thickness of the container 7 was 3.80 mm.

150 ml of water was put into the container 7, and the lid was closed. The container was sealed so that no water leaked out. The vessel was placed in a 500 W microwave oven and heated for 3 minutes to boil water. Immediately after heating, the vessel was taken out of the microwave oven with bare hands. The vessel did not change by heating. In order to confirm, the bottom thickness of the container was measured and found to be 3.95 mm. Heated vessels in microwave ovens increased only 4% in thickness. Therefore, it could be seen that substantially no deformation was caused.

Example 51

Films were laminated using the foam sheet obtained in Example 50, using a polypropylene resin film having a thickness of 100 mu as a non-foaming film, and using an ethylene-vinyl acetate interpolymer as the adhesive.

One side of the polyester resin film was applied with an ethylene-vinyl acetate hybrid polymer resin. The coated side of the film was placed on the polyester resin foam sheet obtained in Example 50.

They were laminated by passing them through a pair of rollers.

The roller temperature of the foam sheet width was room temperature, while the roller temperature of the non-foam film width was 125 ° C.

250 x 250 mm of the sample was cut out to the laminated sheet obtained above, and the foamed sheet surface was brought into contact with a heating plate having a surface temperature of 140 ° C, and the non-foamed film surface was brought into contact with a heating plate having a surface temperature of 100 ° C for 6 seconds. . Subsequently, the foam sheet surface was brought into contact with a female die preheated to 140 ° C., and the non-foamed film surface was allowed to stand for 8 seconds with a male die heated to 100 ° C., whereby the composite sheet could be molded into the same container as in Example 50. And at the same time accelerated the crystallinity. Immediately thereafter, the vessel was placed between two dies of the same shape as the preheated die and cooled for 6 seconds at room temperature. The non-foamed film was molded in such a manner that it was placed inside the container. The molding swelled the foam sheet and the bottom thickness of the vessel was 2.94 mm.

Water was placed in the resulting vessel in the same manner as in Example 50. Immediately after the vessel was heated in the first stage and in the oven, the vessel could be taken out with bare hands. There was no deformation after heating. In order to confirm, it was 3.05 mm when the container bottom thickness was measured. The thickness increase was only 4%. Therefore, this vessel was said to be very resistant to heat in microwave ovens.

Example 52

The foamed sheet obtained in Example 50 was used, and a non-foaming film was used for the polyethylene terephthalate film of thickness 150 micrometers. The composite sheets were obtained by laminating them together without using any adhesives. Lamination of the film was performed using a pair of rollers in which the roller temperature of the foam sheet width was room temperature and the roller temperature of the non-foamed film width was 155 ° C.

250 x 250 mm was cut from the laminated sheet. A container was prepared from the sample in the same manner as in Example 50.

The bottom thickness of the vessel expanded to 4.39 mm.

Water was put in the container. The sprouts were heated in a microwave oven in the same manner as in Example 50. Immediately after heating, the container was taken out from the oven with bare hands. The vessel could not observe any deformation. In order to confirm, the thickness of the bottom of the container was measured and found to be 4.44 mm. The strain was very small at 1%.

Example 53

The procedure of Example 52 was repeated except that a polybutylene terephthalate resin film having a thickness of 30 µ was used instead of the polyethylene terephthalate resin film. The thickness of the bottom of the molded container was 4.02 mm.

After heating, the container could be taken out with bare hands from a microwave oven. The container was not deformed at all compared to before the heat.

The thickness of the bottom of the container after heating was 4.34 mm as a result of measurement. The thickness strain was only 3%.

Comparative Example 17 A container was obtained only from the polyester resin foam sheet obtained in Example 50 without laminating a non-foaming film on the foam sheet. That is, the polyester resin foam sheet obtained in Example 50 was preheated to the contact sheet for 6 seconds with the heating plate heated to 140 ° C. Subsequently, it was left to stand for 8 bags between a sudie heated to 180 ° C. and an arm die heated to 180 ° C. to accelerate molding and crystallization. Immediately thereafter, the molding was placed between a male die and a female die of the same shape as the die heated to 180 ° C. at room temperature and allowed to cool for 6 seconds. This gave the same container as in Example 50 with a bottom thickness of 3.39 mm. Water in the vessel was added in the same manner as in Example 50 and heated in a microwave oven. Immediately after heating, the container was taken out of the microwave oven with bare hands. The removed container had a great expansion and was rugged inside. The bottom thickness of the container after heating was 4.04 mm as a result of the measurement. In other words, the thickness increased by 19%. Therefore, it was found that the large shape of the container could not withstand the heat of the microwave oven.

[Comparative Example 18]

Here, the foam sheet of polystyrene and the non-foaming film of thermoplastic polyester resin were used. The ethylene-vinyl acetate interpolymer resins were used to laminate them together to obtain a laminate sheet corresponding to that described in JP-A-62-70037.

That is, one side of a 50 micron-thick non-foamable polyethylene terephthalate film was coat | covered with interpolymer resin. Thickness 2.4mm, reference weight 200g / cm The coated side of the film was placed on a phosphorus expanded polyethylene sheet and laminated.

Lamination was carried out using a pair of rollers heated to 150 ° C.

250 x 250 mm of sample was cut out from this laminated sheet, and it was preheated by contacting it with the heating plate heated at 140 degreeC for 8 second. Immediately thereafter, it was allowed to stand for 6 seconds at room temperature between the sudai and the amdai, followed by cooling. A container of the same shape as the container of Example 50 was obtained. The container was made in such a way that the non-foaming film was located on the inner surface of the container. The bottom thickness of the vessel increased to 4.2 mm.

Water was placed in the vessel in the same manner as in Example 50 and the vessel was heated in a microwave oven. Immediately after heating, the container was taken out of the microwave oven with bare hands, but was severely deformed by heating.

In particular, the expanded polystyrene layer on the container surface was modified by expansion. As a result, the non-foamed film image on the inner surface of the container was bumpy.

It was 4.88 mm when the bottom thickness of the container after heating was measured. This showed a 16% increase in thickness. Thus, the vessel was found to be unsuitable for use in microwave ovens.

[Effects of the Invention]

As described above, the present invention has the following effects.

The thermoplastic polyester resin foam has a fine cell uniformly dispersed therein.

The foam of the present invention is light in weight, excellent in strength and heat resistance, and, when the foam is high in re-heating, very fine cells are dispersed therein and give a high foaming foam.

The extruded foam sheet of the present invention is excellent in thermoforming. Thermoformed food containers can be used in ovens.

As described above, the present invention has been described in detail with reference to Examples and Reference Examples, but various modifications and adaptations can be made without departing from the object of the present invention.

Claims (24)

A method for producing a thermoplastic polyester resin foam in which a thermoplastic polyester resin is melted, the melted resin is mixed with a foam, and the mixture is extruded with a low pressure paper, wherein the extruded foam is cooled to have a crystallinity of at least 7%. A method of producing a thermoplastic polyester resin crystalline foam, wherein the compound having two or more acid anhydride groups per molecule is added to the thermoplastic polyester resin. The method for producing a thermoplastic polyester resin crystalline foam according to claim 1, wherein the compound having two or more acid anhydride groups per molecule is added at a ratio of 0.05 to 5 parts by weight based on 100 parts by weight of the thermoplastic polyester resin. The compound of claim 1, wherein the compound having at least two acid anhydride groups per molecule is divalent anhydrous pyromellitic acid, dibenzoic benzophenonetetracarboxylic acid, dihydrocyclopentane-tetracarboxylic acid, dianhydrous diphenyl sulfone tetracarboxylic acid, or dianhydride 5 A method for producing a thermoplastic polyester resin crystalline foam which is-(2,5-dioxotetrahydro-3-furyl) -3-methyl-3-cyclohexyl-1,2-dicarboxylic acid. The method for producing a thermoplastic polyester resin crystalline foam according to claim 1, wherein the foam has a density of 0.7 g / cm 3 or less. The method for producing a thermoplastic polyester resin crystalline foam according to claim 1, wherein the foam is an extruded foam sheet having a density of 0.5 g / cm 3 or less. The thermoplastic polyester resin of claim 1 wherein the thermoplastic polyester resin is polyethylene terephthalate, polybutylene terephthalate, polybutylene terephthalate elastomer, amorphous polyester, polycyclohexane terephthalate, polyethylene terephthalate or mixtures thereof. Method for producing a polyester crystalline resin foam. A method for producing a thermoplastic polyester resin foam in which a thermoplastic polyester resin is melted, the melted resin is mixed with a blowing agent, and then the mixture is extruded and molded into a low pressure paper, wherein the compound and the periodic table have two or more acid anhydride groups per molecule. A method for producing a thermoplastic polyester resin foam, wherein a compound of a Group I, Group II, or Group III metal of the phase is added to the thermoplastic polyester resin. 8. The compound according to claim 7, wherein the compound having two or more acid anhydride groups per molecule is used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the thermoplastic polyester resin, and the metals of Group I, Group II, or Group III on the periodic table The manufacturing method of the thermoplastic polyester resin foam which uses 0.05-5 weight part of compounds with respect to 100 weight part of thermoplastic polyester resins. The method for producing a thermoplastic polyester resin foam according to claim 7, wherein the metal compound is a metal compound of Group I on the periodic table. The method for producing a thermoplastic polyester resin foam according to claim 7, wherein the foam has a density of 0.5 g / cm 3 or less. The method for producing a thermoplastic polyester resin crystalline foam according to claim 1, wherein the molten resin is a mixture of the foam and the expansion nucleating agent. The method for producing a thermoplastic resin crystalline foam according to claim 1, wherein the die swell ratio of the thermoplastic resin is 2 to 5. The thermoplastic resin crystalline foam according to claim 1, wherein the thermoplastic resin crystalline foam which pelletizes the mixture which melt-mixed the compound which has two or more acid anhydrides per molecule with a thermoplastic resin previously, mixes the pellet with the said thermoplastic polyester resin. Manufacturing method. 8. A mixture according to claim 7, wherein the compound having at least two acid anhydride groups per molecule is pelletized by a mixture of a metal compound of Group I, Group II, or Group III on the periodic table previously melt mixed with a thermoplastic resin, The manufacturing method of the thermoplastic resin crystalline polyester foaming agent which mixes this pellet with thermoplastic polyester resin. The method for producing a thermoplastic polyester resin crystalline foam according to claim 1, wherein the cooling foam is heated to 60 ° C. or higher and then expanded. The method for producing a thermoplastic polyester resin crystalline foam according to claim 15, wherein a density of the foam cooled below the glass transition temperature of the resin is 0.5 g / cm 3 or less. The method for producing a thermoplastic polyester resin crystalline foam according to claim 15, wherein the polyester resin foam is heated in contact with steam or hot water. The method for producing a thermoplastic polyester resin crystalline foam according to claim 15, wherein the polyester resin foam is heated in contact with a heating plate. The method for producing a thermoplastic polyester resin crystalline foam according to claim 15, wherein the foam is expanded at least 1.3 times by heating. The method for producing a thermoplastic polyester resin crystalline foam according to claim 7, wherein the extruded foam is cooled, and the cooled foam is reheated to 60 ° C or more. The method for producing a thermoplastic polyester resin foam according to claim 20, wherein a density of the foam cooled to a temperature below the glass transition temperature of the resin is 0.5 g / cm 3 or less. 21. The method for producing a thermoplastic polyester resin foam according to claim 20, wherein the polyester resin foam is heated in contact with steam or hot water. The method for producing a thermoplastic polyester resin foam according to claim 20, wherein the heating operation is carried out by bringing the polyester resin foam into contact with a heating plate. 21. The method for producing a thermoplastic polyester resin foam according to claim 20, wherein the foam is heated and re-expanded by 1.3 times or more.

Images